WO2010032790A1 - アンモニア分解触媒およびその製造方法、ならびに、アンモニア処理方法 - Google Patents

アンモニア分解触媒およびその製造方法、ならびに、アンモニア処理方法 Download PDF

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WO2010032790A1
WO2010032790A1 PCT/JP2009/066268 JP2009066268W WO2010032790A1 WO 2010032790 A1 WO2010032790 A1 WO 2010032790A1 JP 2009066268 W JP2009066268 W JP 2009066268W WO 2010032790 A1 WO2010032790 A1 WO 2010032790A1
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ammonia
catalyst
ammonia decomposition
decomposition catalyst
nitrogen
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PCT/JP2009/066268
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English (en)
French (fr)
Japanese (ja)
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岡村　淳志
賢 桐敷
吉宗　壮基
英昭 常木
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株式会社日本触媒
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Priority to US13/119,498 priority Critical patent/US20110176988A1/en
Priority to CN200980136586.1A priority patent/CN102159314B/zh
Priority to EP09814634.3A priority patent/EP2332646B1/de
Publication of WO2010032790A1 publication Critical patent/WO2010032790A1/ja

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    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/02—Preparation of nitrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
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    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • the present invention relates to a catalyst for decomposing ammonia into nitrogen and hydrogen, a method for producing the catalyst, and an ammonia treatment method using the catalyst.
  • Ammonia has an odorous property, particularly an irritating malodor, and therefore it is necessary to treat it if it is contained in the gas above the odor threshold. Therefore, various ammonia treatment methods have been conventionally studied. For example, a method in which ammonia is brought into contact with oxygen and oxidized into nitrogen and water, and a method in which ammonia is decomposed into nitrogen and hydrogen have been proposed.
  • Patent Document 1 for example, a platinum-alumina catalyst, a manganese-alumina catalyst, a cobalt-alumina catalyst, etc. are used for oxidizing ammonia generated from a coke oven into nitrogen and water.
  • a platinum-alumina catalyst, a manganese-alumina catalyst, a cobalt-alumina catalyst, etc. are used for oxidizing ammonia generated from a coke oven into nitrogen and water.
  • an ammonia treatment method using an iron-alumina catalyst, a nickel-alumina catalyst or the like is disclosed.
  • this ammonia treatment method is not preferable because NOx is often produced as a by-product and a new NOx treatment facility is required.
  • Patent Document 2 discloses that nickel or nickel oxide is deposited on a metal oxide carrier such as alumina, silica, titania, zirconia in decomposing ammonia generated from a process of treating organic waste into nitrogen and hydrogen.
  • a metal oxide carrier such as alumina, silica, titania, zirconia
  • An ammonia treatment method using a catalyst that is supported and further added with at least one of an alkaline earth metal and a lanthanoid element in the form of a metal or an oxide is disclosed.
  • this ammonia treatment method has a low ammonia decomposition rate and is not practical.
  • Patent Document 3 discloses an ammonia treatment method using a catalyst in which an alkali metal or an alkaline earth metal basic compound is added to ruthenium on an alumina support in decomposing ammonia generated from a coke oven into nitrogen and hydrogen. It is disclosed.
  • this ammonia treatment method has the advantage that ammonia can be decomposed at a lower temperature than conventional catalysts such as iron-alumina, ruthenium, which is a rare noble metal, is used as an active metal species. It has a big problem in cost and is not practical.
  • Patent Document 4 discloses an iron-ceria complex
  • Patent Document 5 discloses Nickel-lanthanum oxide / alumina, nickel-yttria / alumina, nickel-ceria / alumina ternary composites are disclosed
  • Non-Patent Document 1 discloses an iron-ceria / zirconia ternary composite. ing.
  • any of these catalysts has a low ammonia concentration in the processing gas (specifically, 5% by volume in Patent Document 4 and 50% by volume in Patent Document 5), or a space velocity based on ammonia.
  • Patent Document 4 has 642 h -1
  • Patent Document 5 has 1,000 h -1
  • Non-Patent Document 1 has 430 h -1
  • the ammonia decomposition rate is measured. Even if the ammonia decomposition rate is 100% at a relatively low temperature, the catalyst performance is not necessarily high.
  • each of the conventional ammonia decomposition catalysts has a problem that it cannot obtain high-purity hydrogen by efficiently decomposing ammonia at a relatively low temperature and at a high space velocity.
  • the problem to be solved by the present invention is that ammonia is used at a relatively low temperature in a wide ammonia concentration range from a low concentration to a high concentration without using a noble metal that has practical problems in terms of cost.
  • Another object of the present invention is to provide a catalyst that can be efficiently decomposed into nitrogen and hydrogen at a high space velocity to obtain high purity hydrogen, a method for producing the catalyst, and an ammonia treatment method.
  • the inventors have made it possible to efficiently decompose ammonia into nitrogen and hydrogen at a relatively low temperature and at a high space velocity by adding a specific transition metal to the catalytically active component.
  • the present inventors have found that a catalyst capable of obtaining the hydrogen of the above can be obtained.
  • the present invention is a catalyst for decomposing ammonia into nitrogen and hydrogen
  • the catalytically active component is at least one selected from the group consisting of molybdenum, tungsten, vanadium, chromium, manganese, iron, cobalt, and nickel.
  • An ammonia decomposition catalyst characterized by containing a transition metal of
  • the present inventors have found that when an oxide containing a specific transition metal (excluding a noble metal) is treated with ammonia gas or a nitrogen-hydrogen mixed gas at a predetermined temperature, the ammonia is relatively reduced.
  • the present invention was completed by finding that a catalyst capable of efficiently decomposing nitrogen and hydrogen at a low temperature and at a high space velocity to obtain high purity hydrogen was obtained.
  • the present invention is a catalyst for decomposing ammonia into nitrogen and hydrogen, and the catalytically active component contains at least one selected from the group consisting of molybdenum, tungsten and vanadium (hereinafter referred to as “component A”).
  • component A molybdenum, tungsten and vanadium
  • component B cobalt, nickel, manganese and iron
  • the A component and the B component are more preferably in the form of a composite oxide.
  • the catalytically active component may further contain at least one selected from the group consisting of alkali metals, alkaline earth metals and rare earth metals (hereinafter referred to as “C component”). Furthermore, part or all of the catalytically active component may be treated with ammonia gas or a nitrogen-hydrogen mixed gas.
  • the oxide is mixed with ammonia gas or nitrogen-hydrogen at a temperature of 300 to 800 ° C.
  • the ammonia decomposition catalyst (I) obtained by this production method a part or all of the catalytically active component is changed to a nitride containing an A component or a nitride containing an A component and a B component.
  • the present invention is characterized in that the ammonia-decomposing catalyst (I) as described above is used to treat a gas containing ammonia to decompose the ammonia into nitrogen and hydrogen to obtain hydrogen.
  • An ammonia treatment method is provided.
  • the present inventors have found that when a nitride of a specific transition metal (excluding noble metals) is contained in the catalytically active component, ammonia and nitrogen and hydrogen can be dissolved at a relatively low temperature and at a high space velocity.
  • the present invention was completed by finding that a catalyst capable of obtaining high-purity hydrogen by efficiently decomposing was obtained.
  • the present invention provides an ammonia decomposition catalyst (II) which is a catalyst for decomposing ammonia into nitrogen and hydrogen, and the catalytically active component contains a metal nitride.
  • the catalytically active component contains a nitride of at least one transition metal selected from the group consisting of molybdenum, tungsten, vanadium, chromium, manganese, iron, cobalt, and nickel.
  • it may further contain at least one selected from the group consisting of alkali metals, alkaline earth metals and rare earth metals.
  • the present invention also provides a method for producing an ammonia decomposition catalyst (II), characterized in that a metal nitride precursor is nitrided with ammonia or a nitrogen-hydrogen mixed gas to form the metal nitride.
  • the precursor is at least one transition metal selected from the group consisting of molybdenum, tungsten, vanadium, chromium, manganese, iron, cobalt, and nickel, or a compound thereof. It is preferable that Further, at least one compound selected from the group consisting of alkali metals, alkaline earth metals and rare earth metals may be added to the precursor.
  • the present invention is characterized in that the ammonia-decomposing catalyst (II) as described above is used to treat a gas containing ammonia to decompose the ammonia into nitrogen and hydrogen to obtain hydrogen.
  • An ammonia treatment method is provided.
  • the inventors of the present invention when combining an iron group metal with a metal oxide, efficiently decomposes ammonia into nitrogen and hydrogen at a relatively low temperature and at a high space velocity, thereby producing high purity hydrogen.
  • the present invention has been completed by finding that a catalyst capable of obtaining the above can be obtained.
  • the present invention is a catalyst for decomposing ammonia into nitrogen and hydrogen, wherein the catalytically active component comprises at least one iron group metal and metal oxide selected from the group consisting of iron, cobalt and nickel.
  • the ammonia decomposition catalyst (III) characterized by containing.
  • the metal oxide is preferably at least one selected from the group consisting of ceria, zirconia, yttria, lanthanum oxide, alumina, magnesia, tungsten oxide and titania.
  • the catalytically active component may further contain an alkali metal and / or an alkaline earth metal.
  • the present invention provides a process for producing an ammonia decomposition catalyst (III), wherein an iron group metal compound is supported on a metal oxide, and then the compound is reduced to form the iron group metal.
  • the reduction treatment is preferably performed at a temperature of 300 to 800 ° C. with a reducing gas.
  • the present invention is characterized in that the ammonia-decomposing catalyst (III) as described above is used to treat the ammonia-containing gas and decompose the ammonia into nitrogen and hydrogen to obtain hydrogen.
  • An ammonia treatment method is provided.
  • ammonia is efficiently decomposed into nitrogen and hydrogen at a relatively low temperature and at a high space velocity in a wide ammonia concentration range from a low concentration to a high concentration without using noble metals.
  • a catalyst capable of obtaining pure hydrogen a method for easily producing the catalyst, and a method for obtaining hydrogen by decomposing ammonia into nitrogen and hydrogen using the catalyst.
  • 3 is an X-ray diffraction pattern of a catalyst produced in Experimental Example II-12.
  • 2 is an X-ray diffraction pattern of a catalyst produced in Experimental Example II-16.
  • 3 is an X-ray diffraction pattern of catalyst 11 produced in Experimental Example III-11.
  • 3 is an X-ray diffraction pattern of catalyst 12 produced in Experimental Example III-12.
  • 2 is an X-ray diffraction pattern of catalyst 25 produced in Experimental Example III-25.
  • the ammonia decomposition catalyst (I) of the present invention (hereinafter sometimes referred to as “the catalyst (I) of the present invention”) is a catalyst that decomposes ammonia into nitrogen and hydrogen, and the catalytically active components are molybdenum, tungsten, and It contains at least one selected from the group consisting of vanadium (hereinafter referred to as “component A”).
  • the catalytically active component further contains at least one selected from the group consisting of cobalt, nickel, manganese and iron (hereinafter referred to as “B component”) in addition to the A component.
  • B component cobalt, nickel, manganese and iron
  • the component A and the component B are more preferably in the form of a complex oxide.
  • the catalytically active component is further at least one selected from the group consisting of alkali metals, alkaline earth metals and rare earth metals (hereinafter “C component”) may be contained.
  • catalytically active components may be treated with ammonia gas or a nitrogen-hydrogen mixed gas.
  • the catalytically active component contains at least one selected from the group consisting of molybdenum, tungsten and vanadium as the A component. Of these components A, molybdenum and tungsten are preferable, and molybdenum is more preferable.
  • the starting material for the component A is not particularly limited as long as it is usually used as a starting material for the catalyst, but is preferably an inorganic compound such as an oxide, chloride, ammonium salt, alkali metal salt; And organic acid salts such as acetate and oxalate; organometallic complexes such as acetylacetonate complex and metal alkoxide; and the like.
  • an inorganic compound such as an oxide, chloride, ammonium salt, alkali metal salt
  • organic acid salts such as acetate and oxalate
  • organometallic complexes such as acetylacetonate complex and metal alkoxide; and the like.
  • the molybdenum source for example, molybdenum oxide, ammonium molybdate, sodium molybdate, potassium molybdate, rubidium molybdate, cesium molybdate, lithium molybdate, molybdenum 2-ethylhexylate, bis (acetylacetonato) ) Oxomolybdenum and the like, and ammonium molybdate is preferred.
  • the tungsten source include tungsten oxide, ammonium tungstate, sodium tungstate, potassium tungstate, rubidium tungstate, lithium tungstate, tungsten ethoxide, and the like, and ammonium tungstate is preferable.
  • vanadium source examples include vanadium oxide, ammonium vanadate, sodium vanadate, lithium vanadate, bis (acetylacetonato) oxovanadium, vanadium oxytriethoxide, vanadium oxytriisopropoxide, and vanadic acid. Ammonium is preferred.
  • the component A is an essential element of the catalytically active component, and the content of the component A is preferably 20 to 90% by mass, more preferably 40 to 70% by mass with respect to 100% by mass of the catalytically active component.
  • the catalytically active component preferably contains at least one selected from the group consisting of cobalt, nickel, manganese and iron as the B component. Of these B components, cobalt and nickel are preferable, and cobalt is more preferable.
  • the starting material for the component B is not particularly limited as long as it is usually used as a starting material for the catalyst, but is preferably an inorganic material such as an oxide, hydroxide, nitrate, sulfate, or carbonate.
  • an inorganic material such as an oxide, hydroxide, nitrate, sulfate, or carbonate.
  • examples of the cobalt source include cobalt oxide, cobalt hydroxide, cobalt nitrate, cobalt sulfate, ammonium cobalt sulfate, cobalt carbonate, cobalt acetate, cobalt oxalate, cobalt citrate, cobalt benzoate, and 2-ethylhexyl acid.
  • Examples include cobalt and lithium cobalt oxide, and cobalt nitrate is preferable.
  • nickel source examples include nickel oxide, nickel hydroxide, nickel nitrate, nickel sulfate, nickel carbonate, nickel acetate, nickel oxalate, nickel citrate, nickel benzoate, nickel 2-ethylhexylate, and bis (acetylacetonate). Nickel etc. are mentioned, Nickel nitrate is preferable.
  • the manganese source examples include manganese oxide, manganese nitrate, manganese sulfate, manganese carbonate, manganese acetate, manganese citrate, manganese 2-ethylhexylate, potassium permanganate, sodium permanganate, cesium permanganate and the like.
  • Manganese nitrate is preferred.
  • the iron source examples include iron oxide, iron hydroxide, iron nitrate, iron sulfate, iron acetate, iron oxalate, iron citrate, and iron methoxide, and iron nitrate is preferable.
  • the content of the component B is preferably 0 to 50% by mass, more preferably 10 to 40% by mass with respect to 100% by mass of the catalytically active component.
  • the A component and the B component are used in combination, as a starting material of the A component and the B component, for example, a mixture of an oxide of the A component and an oxide of the B component, or a composite of the A component and the B component An oxide can be used.
  • Specific examples of the composite oxide of the A component and the B component are not particularly limited, and examples thereof include CoMoO 4 , NiMoO 4 , MnMoO 4 , and CoWO 4 .
  • the catalytically active component may contain at least one selected from the group consisting of alkali metals, alkaline earth metals, and rare earth metals as the C component. Of these C components, alkali metals and alkaline earth metals are preferred, and alkali metals are more preferred.
  • the starting material of component C is not particularly limited as long as it is usually used as a starting material for the catalyst, but is preferably an oxide, hydroxide, nitrate, sulfate, carbonate, acetate. And oxalate.
  • the content of component C is preferably 0 to 50% by mass, more preferably 0.2 to 20% by mass with respect to 100% by mass of the catalytically active component.
  • a component oxide, a mixture of an A component oxide and a B component oxide, a composite oxide of A component and B component, a mixture obtained by adding an oxide of C component to these, or these A method of using, as a catalyst, a calcined product obtained by calcining a mixture obtained by adding an aqueous solution of the component C to a dried product; (2) A method in which the fired product of (1) is further treated (nitrided) with ammonia gas or a nitrogen-hydrogen mixed gas at a temperature of 300 to 800 ° C .; (3) A method in which an aqueous solution of a salt containing the component A is calcined to form an oxide, and the oxide is used as a catalyst; (4) A method of further treating (nitriding) the oxide of (3) with ammonia gas or a nitrogen-hydrogen mixed gas at a temperature of 300 to 800 ° C .; (5) A method in which an aqueous solution of a salt containing an A component and a salt containing a B
  • the method for producing an ammonia decomposition catalyst (I) according to the present invention comprises an oxide containing an A component or an oxide containing an A component and a B component. Then, the oxide is treated (nitrided) with ammonia gas or a nitrogen-hydrogen mixed gas at a temperature of 300 to 800 ° C. In addition, you may add the compound of C component after preparing the said oxide.
  • the temperature of the nitriding treatment is usually 300 to 800 ° C., preferably 400 to 750 ° C., more preferably 500 to 720 ° C.
  • the concentration is preferably 10 to 100% by volume, more preferably 50 to 100% by volume.
  • the concentration of nitrogen is preferably 2 to 95% by volume, more preferably 20 to 90% by volume.
  • the concentration of hydrogen is preferably 5 to 98% by volume, more preferably 10 to 80% by volume.
  • the flow rate (volume) of the gas is preferably 80 to 250 times, more preferably 100 to 200 times the volume of the catalyst per minute in either case of ammonia gas or nitrogen-hydrogen mixed gas.
  • the flow rate (volume) of nitrogen is preferably 50 to 120 times, more preferably 60 to 100 times the volume of the catalyst per minute.
  • the ratio of the catalytically active component changed to nitride by the nitriding treatment can be confirmed by examining the crystal structure of the catalyst by X-ray diffraction. Although it is preferable that all of the catalytically active component is changed to nitride, it is not always necessary, and even if a part of the catalytically active component is changed to nitride, it has sufficient catalytic activity. .
  • the ratio of nitride in the catalyst is preferably 3% or more, more preferably 5% That's it.
  • the ammonia decomposition catalyst (II) of the present invention (hereinafter sometimes referred to as “the catalyst (II) of the present invention”) is a catalyst that decomposes ammonia into nitrogen and hydrogen, and the catalytically active component contains a metal nitride. It is characterized by doing.
  • the metal nitride is not particularly limited as long as it is a transition metal nitride.
  • the transition metal nitride belonging to Groups 4 to 8 of the periodic table is used. Is mentioned.
  • it is preferably a nitride of at least one transition metal selected from the group consisting of molybdenum, cobalt, nickel, iron, vanadium, tungsten, chromium and manganese, and molybdenum, cobalt, nickel And nitrides of at least one transition metal selected from the group consisting of iron and iron are more preferred.
  • the metal nitride may be used by itself or may be formed by nitriding the precursor with ammonia gas or a nitrogen-hydrogen mixed gas.
  • the metal nitride precursor include transition metals, oxides and salts thereof. Of these precursors, transition metal oxides are preferred.
  • the transition metal is as described above.
  • the ratio of the catalytically active component changed to nitride by the nitriding treatment can be confirmed by examining the crystal structure of the catalyst by X-ray diffraction. Although it is preferable that all of the catalytically active component is changed to nitride, it is not always necessary, and even if a part of the catalytically active component is changed to nitride, it has sufficient catalytic activity. .
  • the ratio of nitride in the catalyst is preferably 3% or more, more preferably 5% That's it.
  • the catalytically active component may further contain at least one selected from the group consisting of alkali metals, alkaline earth metals and rare earth metals. Of these additive components, alkali metals are preferred.
  • the amount of these additive components is preferably 0 to 50% by mass, more preferably 0.2 to 20% by mass with respect to the metal nitride.
  • rare earth metals are converted as trivalent metal oxides, alkali metals as monovalent metal oxides, and alkaline earth metals as divalent metal oxides.
  • a method of nitriding a metal nitride precursor with ammonia gas (2) A method of nitriding a metal nitride precursor with a nitrogen-hydrogen mixed gas; (3) A method in which an additive component is mixed and contained in a metal nitride precursor and then nitriding with ammonia gas or nitrogen-hydrogen mixed gas; (4) An aqueous solution or aqueous suspension containing an additive component is mixed with the precursor of the metal nitride, dried, and if necessary, calcined and then subjected to nitriding with ammonia gas or nitrogen-hydrogen mixed gas Method; (5) A method in which a metal nitride precursor is nitrided with ammonia gas or a nitrogen-hydrogen mixed gas and then mixed with an additional component; (6) After nitriding the precursor of metal nitride with ammonia gas or nitrogen-hydrogen mixed gas, an aqueous solution or aqueous suspension containing additive components is mixed
  • the method for producing an ammonia decomposition catalyst (II) according to the present invention includes, for example, nitriding a metal nitride precursor with ammonia gas or a nitrogen-hydrogen mixed gas.
  • the metal nitride is formed by processing.
  • the metal nitride precursor is preferably at least one transition metal selected from the group consisting of molybdenum, cobalt, nickel, iron, vanadium, tungsten, chromium and manganese, or a compound thereof. Further, at least one compound selected from the group consisting of alkali metals, alkaline earth metals, and rare earth metals may be added to the metal nitride precursor. Of these additive components, alkali metals are preferred.
  • the metal nitride is used by itself or is formed by nitriding the precursor with ammonia gas or nitrogen-hydrogen mixed gas.
  • the metal nitride precursor include transition metals, oxides and salts thereof. Of these precursors, transition metal oxides are preferred.
  • the transition metal is as described above.
  • the temperature of the nitriding treatment is usually 300 to 800 ° C., preferably 400 to 750 ° C., more preferably 500 to 720 ° C.
  • ammonia the ammonia concentration is preferably 10 to 100% by volume, more preferably 50 to 100% by volume.
  • concentration of nitrogen is preferably 2 to 95% by volume, more preferably 20 to 90% by volume.
  • concentration of hydrogen is preferably 5 to 98% by volume, more preferably 10 to 80% by volume.
  • the flow rate (volume) of the gas is preferably 80 to 250 times, more preferably 100 to 200 times the volume of the catalyst per minute in either case of ammonia or a nitrogen-hydrogen mixed gas.
  • the flow rate (volume) of nitrogen is preferably 50 to 120 times, more preferably 60 to 100 times the volume of the catalyst per minute.
  • ammonia decomposition catalyst (III) ⁇ Ammonia decomposition catalyst (III) ⁇
  • the ammonia decomposition catalyst (III) of the present invention is characterized in that the catalytically active component contains an iron group metal and a metal oxide.
  • iron group metal at least one selected from the group consisting of cobalt, nickel and iron is used. Of these iron group metals, cobalt and nickel are preferable, and cobalt is more preferable.
  • the starting material for the iron group metal is not particularly limited as long as it is usually used as a starting material for the catalyst, but preferably, oxides, hydroxides, nitrates, sulfates, carbonates, etc.
  • Inorganic compounds organic acid salts such as acetates and oxalates; organometallic complexes such as acetylacetonato complexes and metal alkoxides;
  • examples of the cobalt source include cobalt oxide, cobalt hydroxide, cobalt nitrate, cobalt sulfate, ammonium cobalt sulfate, cobalt carbonate, cobalt acetate, cobalt oxalate, cobalt citrate, cobalt benzoate, and 2-ethylhexyl acid.
  • Examples include cobalt and lithium cobalt oxide, and cobalt nitrate is preferable.
  • nickel source examples include nickel oxide, nickel hydroxide, nickel nitrate, nickel sulfate, nickel carbonate, nickel acetate, nickel oxalate, nickel citrate, nickel benzoate, nickel 2-ethylhexylate, and bis (acetylacetonate). Nickel etc. are mentioned, Nickel nitrate is preferable.
  • iron source examples include iron oxide, iron hydroxide, iron nitrate, iron sulfate, iron carbonate, iron acetate, iron oxalate, iron citrate, and iron methoxide, and iron nitrate is preferable.
  • the iron group metal is an essential component of the catalytically active component, and the content of the iron group metal is preferably 5 to 90% by mass, more preferably 10 to 80% by mass with respect to 100% by mass of the catalytically active component. .
  • transition metals excluding noble metals
  • typical metals may be added to the iron group metals.
  • transition metals include molybdenum, tungsten, vanadium, chromium, manganese, and the like.
  • typical metals include zinc, gallium, indium, and tin.
  • the starting materials for other transition metals and typical metals are not particularly limited as long as they are usually used as starting materials for catalysts.
  • oxides, hydroxides, nitrates, sulfates, carbonates examples thereof include salts, acetates, oxalates, and organometallic complexes.
  • the metal oxide is not particularly limited, but is preferably at least one selected from the group consisting of ceria, zirconia, yttria, lanthanum oxide, alumina, magnesia, tungsten oxide and titania, More preferred is at least one selected from the group consisting of zirconia, yttria and lanthanum oxide.
  • these metal oxides as the two or more kinds of metal oxides, for example, a mixture of metal oxides, a composite oxide, or a solid solution of metal oxides can be used.
  • ceria, zirconia, solid solution of ceria and zirconia (CeZrO x ), solid solution of ceria and yttria (CeYO x ), solid solution of ceria and lanthanum oxide (CeOO x ) are preferable, and ceria and A solid solution with zirconia (CeZrO x ) is more preferable.
  • the metal oxide is an essential component of the catalytically active component, and the content of the metal oxide is preferably 10 to 95% by mass, more preferably 20 to 90% by mass with respect to 100% by mass of the catalytically active component. .
  • the catalytically active component may further contain an alkali metal and / or an alkaline earth metal (hereinafter sometimes referred to as “additive component”) in addition to the iron group metal and metal oxide.
  • additive component an alkali metal and / or an alkaline earth metal
  • alkali metal examples include lithium, sodium, potassium, cesium and the like. Of these alkali metals, potassium and cesium are preferable.
  • alkaline earth metals examples include magnesium, calcium, strontium, barium and the like. Of these alkaline earth metals, strontium and barium are preferred.
  • the starting material for the additive component is not particularly limited as long as it is usually used as a starting material for the catalyst.
  • hydroxides, nitrates, carbonates, acetates, oxalates, and the like are used. Can be mentioned.
  • the decomposition treatment include a method of decomposing by raising the temperature under a nitrogen stream, and a method of decomposing by raising the temperature under a hydrogen stream. Of these decomposition treatments, a method of decomposing by raising the temperature under a hydrogen stream is preferred.
  • the content of the additive component is preferably 0 to 25% by mass, more preferably 0.2 to 15% by mass, and further preferably 0.4 to less than 10% by mass with respect to 100% by mass of the catalytically active component.
  • an additive may be added to the metal oxide in order to suppress aggregation of the catalyst particles.
  • it is effective to select a combination that does not form a solid solution with each other from the metal oxide and the additive.
  • a solid solution of ceria and zirconia (CeZrO x ) is used as the metal oxide
  • an alkaline earth metal such as magnesium or calcium
  • a metal oxide such as silica or alumina.
  • a method in which an aqueous solution of an iron group metal compound is impregnated in a metal oxide, dried, calcined with an inert gas, and then reduced with a reducing gas (2) A method in which an aqueous solution of an iron group metal compound is impregnated in a metal oxide, dried, subjected to a reduction treatment using a water-soluble reducing agent, filtered, and dried; (3) An aqueous solution containing additive components is added to the metal oxide and dried, then impregnated with an aqueous solution of an iron group metal compound, dried, calcined with an inert gas, and then reduced with a reducing gas.
  • An aqueous solution of an iron group metal compound is impregnated in a metal oxide and dried. Further, an aqueous solution of an iron group metal compound is impregnated in a metal oxide, dried, and then calcined with an inert gas. Thereafter, a reduction treatment with a reducing gas; (5) An aqueous solution of an iron group metal compound is impregnated into a metal oxide, dried, calcined with an inert gas, then reduced with a reducing gas, an aqueous solution containing an additive component is added, and dried.
  • aqueous solution containing an iron group metal compound and a water-soluble metal salt that is a precursor of the metal oxide is treated with an excess amount of an alkaline aqueous solution (for example, aqueous ammonia, tetramethylammonium hydroxide, potassium hydroxide).
  • an alkaline aqueous solution for example, aqueous ammonia, tetramethylammonium hydroxide, potassium hydroxide.
  • an aqueous solution, etc. with stirring, the solid product obtained is filtered, washed with water, dried and then subjected to a reduction treatment; (7) An excess amount of an alkaline aqueous solution (for example, aqueous ammonia, tetramethylammonium hydroxide, potassium hydroxide) is added to an aqueous solution containing an iron group metal compound and a water-soluble metal salt that is a precursor of the metal oxide. An aqueous solution or the like) is added dropwise with stirring, and the resulting solid product is filtered, washed with water, dried, and then subjected to a reduction treatment.
  • an alkaline aqueous solution for example, aqueous ammonia, tetramethylammonium hydroxide, potassium hydroxide
  • An aqueous solution or the like is added dropwise with stirring, and the resulting solid product is filtered, washed with water, dried, and then subjected to a reduction treatment.
  • the method for producing an ammonia decomposition catalyst (III) according to the present invention is characterized in that an iron group metal compound is reduced to form the iron group metal.
  • the reduction treatment is not particularly limited as long as the iron group metal compound can be formed by reducing the iron group metal compound.
  • a method using a reducing gas such as carbon monoxide, hydrocarbon or hydrogen; a method of adding a reducing agent such as hydrazine, lithium aluminum hydride or tetramethylborohydride;
  • reducing gas can also be diluted and used with other gas (for example, nitrogen, carbon dioxide).
  • reduction treatment using hydrogen as the reducing gas is preferable.
  • heating is preferably performed at a temperature of 300 to 800 ° C, more preferably 400 to 600 ° C.
  • the reduction time is preferably 0.5 to 5 hours, more preferably 1 to 3 hours.
  • an inert gas such as nitrogen or carbon dioxide is used, preferably at a temperature of 200 to 400 ° C., preferably for 1 to 7 hours, more preferably for 3 to 6 hours. It can also be fired.
  • the iron group metal compound When the reduction treatment is performed, the iron group metal compound is converted into an iron group metal showing a metal state of zero valence in principle. If the reduction treatment is insufficient, the iron group metal compound is only partially reduced and the catalyst exhibits low activity. However, even in such a case, since hydrogen is generated during the ammonia decomposition reaction, it becomes the same environment as the state where the reduction treatment is performed. Therefore, by continuing such a reaction, it is insufficiently reduced. The reduction treatment of the remaining portion proceeds to a metal state with a valence of 0, and the catalyst becomes highly active.
  • the catalysts (I), (II) and (III) of the present invention preferably have a specific surface area of 1 to 300 m 2 / g, more preferably 5 to 260 m 2 / g, and still more preferably 18 to 200 m 2 / g. .
  • the “specific surface area” means, for example, a BET specific surface area measured using a fully automatic BET surface area measuring device (product name “Marcsorb HM Model-1201”, manufactured by Mountec Co., Ltd.).
  • the crystallite size of the iron group metal is preferably 3 to 200 nm, more preferably 5 to 150 nm, still more preferably 10 to 100 nm, and the crystallite size of the metal oxide is preferably 2 It is ⁇ 200 nm, more preferably 3 to 100 nm, still more preferably 4 to 25 nm.
  • the crystallite size was measured by assigning the crystal structure to the result of the X-ray diffraction measurement, and calculated from the half width of the peak indicating the maximum intensity using the following Scherrer equation.
  • K is a shape factor (0.9 is substituted as a sphere)
  • ⁇ is a measured X-ray wavelength (CuK ⁇ : 0.154 nm)
  • ⁇ is a half width (rad)
  • ⁇ is a Bragg angle (half of the diffraction angle 2 ⁇ ; deg).
  • the catalytically active component may be used as it is, or the catalytically active component may be supported on a carrier using a conventionally known method.
  • the support is not particularly limited, and examples thereof include metal oxides such as alumina, silica, titania, zirconia, and ceria.
  • the catalysts (I), (II) and (III) of the present invention may be used after being molded into a desired shape using a conventionally known method.
  • the shape of the catalyst is not particularly limited, and examples thereof include granular, spherical, pellet-shaped, crushed, saddle-shaped, ring-shaped, honeycomb-shaped, monolith-shaped, net-shaped, columnar, cylindrical, and the like.
  • the catalysts (I), (II) and (III) of the present invention may be used by coating the surface of the structure in layers.
  • the structure is not particularly limited.
  • a structure made of a ceramic such as cordierite, mullite, silicon carbide, alumina, silica, titania, zirconia, and ceria; a structure made of a metal such as ferritic stainless steel Body; and the like.
  • the shape of the structure is not particularly limited, and examples thereof include a honeycomb shape, a corrugated shape, a net shape, a columnar shape, and a cylindrical shape.
  • the ammonia treatment method of the present invention treats a gas containing ammonia using the ammonia decomposition catalyst (I), (II) or (III) as described above, and decomposes the ammonia into nitrogen and hydrogen. To obtain hydrogen.
  • the “gas containing ammonia” to be treated is not particularly limited, but includes not only ammonia gas and ammonia-containing gas but also gas containing a substance that generates ammonia by thermal decomposition such as urea. There may be. Moreover, the gas containing ammonia may contain other components as long as it does not become a catalyst poison.
  • the flow rate of the "gas containing ammonia” per catalyst is a space velocity, preferably 1,000 ⁇ 200,000 -1, more preferably 2,000 ⁇ 150,000h -1, more preferably 3,000 to 100,000h -1 .
  • the flow rate of the “gas containing ammonia” per catalyst means the volume of the “gas containing ammonia” passing through the catalyst per unit time per volume occupied by the catalyst when the catalyst is charged into the reactor. Means.
  • the reaction temperature is preferably 180 to 950 ° C, more preferably 300 to 900 ° C, still more preferably 400 to 800 ° C.
  • the reaction pressure is preferably 0.002 to 2 MPa, more preferably 0.004 to 1 MPa.
  • high-purity hydrogen can be obtained by separating nitrogen and hydrogen obtained by decomposing ammonia into nitrogen and hydrogen using a conventionally known method. it can.
  • -Ammonia decomposition catalyst (I)- First, production examples and performance evaluation of the ammonia decomposition catalyst (I) will be described.
  • An X-ray diffractometer (product name “RINT-2400”, manufactured by Rigaku Corporation) was used for the X-ray diffraction measurement. CuK ⁇ (0.154 nm) was used as the X-ray source.
  • the measurement conditions were an X-ray output of 50 kV, 300 mA, a divergence slit of 1.0 mm, a divergence length limit slit of 10 mm, a scan speed of 5 degrees per minute, and a sampling width of 0. The measurement was performed at 02 degrees and a scanning range of 5 to 90 degrees.
  • ⁇ -CoMoO 4 ⁇ -CoMoO 4 was charged into a reaction tube made of SUS316, and the temperature was raised to 400 ° C. while flowing 30 to 50 mL / min of nitrogen gas (hereinafter abbreviated as “nitrogen”). Subsequently, while flowing ammonia gas (hereinafter abbreviated as “ammonia”) at 50 to 100 mL / min, the temperature is raised to 700 ° C. and maintained at 700 ° C. for 5 hours (nitriding treatment), and an ammonia decomposition catalyst (hereinafter “ CoMoO 4 ”).
  • nitrogen gas hereinafter abbreviated as “ammonia”
  • Example I-8 In Example I-1, except that cobalt nitrate hexahydrate was changed to nickel nitrate hexahydrate, an ammonia decomposition catalyst (hereinafter referred to as “NiMoO 4 ”) was used in the same manner as in Example I-1. Got. It should be noted that the state after firing at 350 ° C. for 5 hours under a nitrogen stream and after firing at 500 ° C. for 3 hours under an air stream was confirmed to be NiMoO 4 showing ⁇ -CoMoO 4 type by X-ray diffraction measurement. did.
  • NiMoO 4 ammonia decomposition catalyst
  • Experimental Example I-9 In Experimental Example I-8, the state after calcination at 350 ° C. for 5 hours under a nitrogen stream and after calcination at 500 ° C. for 3 hours under an air stream is the state of NiMoO 4 showing ⁇ -CoMoO 4 type by X-ray diffraction measurement. After confirming that, an aqueous solution in which 0.075 g of cesium nitrate was dissolved in 1.55 g of distilled water was dropped into NiMoO 4 showing ⁇ -CoMoO 4 type, and the solution was uniformly permeated at 90 ° C.
  • An ammonia decomposition catalyst (hereinafter referred to as “1% Cs—NiMoO 4 ”) was obtained in the same manner as in Experimental Example I-8, except that nitriding treatment was performed after drying for 10 hours. The state before the nitriding treatment was confirmed to be NiMoO 4 showing ⁇ -CoMoO 4 type by X-ray diffraction measurement.
  • Experimental Examples I-10 and I-11 >> In Experimental Example I-9, instead of an aqueous solution in which 0.075 g of cesium nitrate was dissolved in 1.55 g of distilled water, in Experimental Example I-10, an aqueous solution in which 0.15 g of cesium nitrate was dissolved in 1.55 g of distilled water. In Example I-11, an ammonia decomposition catalyst was used in the same manner as in Example I-9, except that an aqueous solution in which 0.40 g of cesium nitrate was dissolved in 1.55 g of distilled water was used. (Hereinafter referred to as “2% Cs—NiMoO 4 ”) and an ammonia decomposition catalyst (hereinafter referred to as “5% Cs—NiMoO 4 ”).
  • Example I-12 ⁇ A reaction tube made of SUS316 was filled with 0.5 to 1.0 mL of commercially available molybdenum oxide (MoO 3 ), and heated to 400 ° C. while flowing nitrogen of 30 to 50 mL / min. Next, the temperature is raised to 700 ° C. while flowing ammonia at 50 to 100 mL / min, and a treatment (nitriding treatment) is performed at 700 ° C. for 5 hours to obtain an ammonia decomposition catalyst (hereinafter referred to as “MoO 3 ”). It was.
  • MoO 3 ammonia decomposition catalyst
  • Experimental Examples I-14 and I-15 >> In Experimental Example I-13, instead of an aqueous solution in which 0.21 g of cesium nitrate was dissolved in 1.62 g of distilled water, in Experimental Example I-14, an aqueous solution in which 0.54 g of cesium nitrate was dissolved in 1.62 g of distilled water. In Example I-15, an ammonia decomposition catalyst was used in the same manner as in Example I-13, except that an aqueous solution in which 1.14 g of cesium nitrate was dissolved in 1.62 g of distilled water was used. (Hereinafter referred to as “5% Cs—MoO 3 ”) and an ammonia decomposition catalyst (hereinafter referred to as “10% Cs—MoO 3 ”).
  • a reaction tube made of SUS316 was filled in a reaction tube made of SUS316, and the temperature was raised to 400 ° C. while flowing 30 to 50 mL / min of nitrogen. Next, the temperature is raised to 700 ° C. while flowing ammonia at 50 to 100 mL / min, and a treatment (nitriding treatment) is performed for 5 hours at 700 ° C. to obtain an ammonia decomposition catalyst (hereinafter referred to as “MnMoO 4 ”). It was.
  • MnMoO 4 ammonia decomposition catalyst
  • a reaction tube made of SUS316 was filled in a reaction tube made of SUS316, and the temperature was raised to 400 ° C. while flowing 30 to 50 mL / min of nitrogen. Next, the temperature is raised to 700 ° C. while flowing ammonia at 50 to 100 mL / min, and a treatment (nitriding treatment) is performed at 700 ° C. for 5 hours to obtain an ammonia decomposition catalyst (hereinafter referred to as “MgMoO 4 ”). It was.
  • MgMoO 4 ammonia decomposition catalyst
  • the ammonia decomposition rate was measured under the conditions of a space velocity of 6,000 h ⁇ 1 , a reaction temperature of 400 ° C., 450 ° C., or 500 ° C., and a reaction pressure of 0.101325 MPa (normal pressure) (calculated by the following formula). did). The results are shown in Table 1.
  • the ammonia decomposition catalysts of Experimental Examples I-1 to I-19 all have a high concentration of 99.9% by volume or more of ammonia at a relatively low temperature of 400 to 500 ° C. In addition, it can be efficiently decomposed into nitrogen and hydrogen at a high space velocity of 6,000 h ⁇ 1 . Further, since the ammonia catalysts of Experimental Examples I-1 to I-11 are composite oxides of molybdenum as the A component and cobalt or nickel as the B component, the ammonia decomposition rate is relatively high.
  • An X-ray diffractometer (product name “RINT-2400”, manufactured by Rigaku Corporation) was used for the X-ray diffraction measurement. CuK ⁇ (0.154 nm) was used as the X-ray source. The measurement conditions were an X-ray output of 50 kV, 300 mA, a divergence slit of 1.0 mm, a divergence length limit slit of 10 mm, a scan speed of 5 degrees per minute, and a sampling width of 0. The measurement was performed at 02 degrees and a scanning range of 5 to 90 degrees.
  • ⁇ -CoMoO 4 ⁇ -CoMoO 4 was charged into a reaction tube made of SUS316, and the temperature was raised to 400 ° C. while flowing 30 to 50 mL / min of nitrogen gas (hereinafter abbreviated as “nitrogen”). Subsequently, while flowing ammonia gas (hereinafter abbreviated as “ammonia”) at 50 to 100 mL / min, the temperature is raised to 700 ° C. and maintained at 700 ° C. for 5 hours (nitriding treatment), and an ammonia decomposition catalyst (hereinafter “ CoMoO 4 ”). X-ray diffraction measurement confirmed that metal nitride was formed (see Table 3). Of the peaks shown in Table 3, peak number 3 seems to be derived from Mo, but all other peaks are peaks derived from Co 3 Mo 3 N.
  • Example II-8 ⁇ an ammonia decomposition catalyst (hereinafter referred to as “NiMoO 4 ”) was used in the same manner as Example II-1 except that cobalt nitrate hexahydrate was changed to nickel nitrate hexahydrate. Got. It should be noted that the state after firing at 350 ° C. for 5 hours under a nitrogen stream and after firing at 500 ° C. for 3 hours under an air stream was confirmed to be NiMoO 4 showing ⁇ -CoMoO 4 type by X-ray diffraction measurement. did. The X-ray diffraction pattern of the obtained ammonia decomposition catalyst is shown in FIG. As is clear from FIG. 1, it can be seen that almost all of them are changed to nitride.
  • An ammonia decomposition catalyst (hereinafter referred to as “1% Cs—NiMoO 4 ”) was obtained in the same manner as in Experimental Example II-8, except that nitriding treatment was performed after drying for 10 hours. The state before the nitriding treatment was confirmed to be NiMoO 4 showing ⁇ -CoMoO 4 type by X-ray diffraction measurement. Although the diffraction pattern of the obtained ammonia decomposition catalyst is not shown in the figure, it was the same as the ammonia decomposition catalyst of Experimental Example 8.
  • Experimental Examples II-10 and II-11 >> In Experimental Example II-9, instead of an aqueous solution in which 0.075 g of cesium nitrate was dissolved in 1.55 g of distilled water, in Experimental Example II-10, an aqueous solution in which 0.15 g of cesium nitrate was dissolved in 1.55 g of distilled water. In Example II-11, an ammonia decomposition catalyst was used in the same manner as in Example II-9, except that an aqueous solution in which 0.40 g of cesium nitrate was dissolved in 1.55 g of distilled water was used.
  • Experimental Examples II-14 and II-15 >> In Experimental Example II-13, instead of an aqueous solution in which 0.21 g of cesium nitrate was dissolved in 1.62 g of distilled water, in Experimental Example II-14, an aqueous solution in which 0.54 g of cesium nitrate was dissolved in 1.62 g of distilled water. In Example II-15, an ammonia decomposition catalyst was used in the same manner as in Example II-13, except that an aqueous solution in which 1.14 g of cesium nitrate was dissolved in 1.62 g of distilled water was used.
  • a reaction tube made of SUS316 was filled in a reaction tube made of SUS316, and the temperature was raised to 400 ° C. while flowing 30 to 50 mL / min of nitrogen. Next, the temperature is raised to 700 ° C. while flowing ammonia at 50 to 100 mL / min, and a treatment (nitriding treatment) is performed for 5 hours at 700 ° C. to obtain an ammonia decomposition catalyst (hereinafter referred to as “MnMoO 4 ”). It was.
  • MnMoO 4 ammonia decomposition catalyst
  • a reaction tube made of SUS316 was filled in a reaction tube made of SUS316, and the temperature was raised to 400 ° C. while flowing 30 to 50 mL / min of nitrogen. Next, the temperature is raised to 700 ° C. while flowing ammonia at 50 to 100 mL / min, and a treatment (nitriding treatment) is performed at 700 ° C. for 5 hours to obtain an ammonia decomposition catalyst (hereinafter referred to as “MgMoO 4 ”). It was.
  • MgMoO 4 ammonia decomposition catalyst
  • the ammonia decomposition rate was measured under the conditions of a space velocity of 6,000 h ⁇ 1 , a reaction temperature of 400 ° C., 450 ° C., or 500 ° C., and a reaction pressure of 0.101325 MPa (normal pressure) (calculated by the following formula). did). The results are shown in Table 10.
  • the ammonia decomposition catalysts of Experimental Examples II-1 to II-19 all had a high concentration of 99.9% by volume or more of ammonia at a relatively low temperature of 400 to 500 ° C. In addition, it can be efficiently decomposed into nitrogen and hydrogen at a high space velocity of 6,000 h ⁇ 1 .
  • the ammonia catalysts of Experimental Examples II-1 to II-11 are complex oxides of molybdenum as component A and cobalt or nickel as component B, the ammonia decomposition rate is relatively high.
  • cesium as the C component is added to the composite oxide of molybdenum as the A component and cobalt as the B component. Is very expensive.
  • ammonia decomposition catalyst (III)- Next, production examples and performance evaluation of the ammonia decomposition catalyst (III) will be described.
  • the specific surface area was measured using a fully automatic BET surface area measuring device (product name “Marcsorb HM Model-1201”, manufactured by Mountec Co., Ltd.). Further, an X-ray diffractometer (product name “X'Pert Pro MPD”, manufactured by Spectris Co., Ltd.) was used for X-ray diffraction measurement and crystallite size measurement. CuK ⁇ (0.154 nm) is used as the X-ray source.
  • X-ray output 45 kV, 40 mA, step size 0.017 °, scan step time 100 seconds, measurement temperature 25 ° C., measurement range should be measured It carried out by selecting suitably according to an iron group metal and a metal oxide. Further, the catalyst composition was quantified by elemental analysis using a fluorescent X-ray analyzer (product name “RIX2000”, manufactured by Rigaku Corporation). The measurement conditions were an X-ray output of 50 kV and 50 mA, and the calculation method used was the FP method (fundamental parameter method).
  • Aqueous solution 1 was obtained by dissolving 1.001 g of cesium nitrate in 5.0476 g of distilled water. 1.4768 g of aqueous solution 1 was added to 2.6787 g of catalyst 1 and mixed, followed by drying at 90 ° C. overnight. To this dried mixture, 1.4804 g of the aqueous solution 1 was added again and mixed, and then dried at 90 ° C. overnight. The dried mixture was baked at 350 ° C. for 5 hours under a nitrogen stream, and then baked at 500 ° C. for 3 hours under an air stream. The fired product was filled in an annular furnace, and reduced at 450 ° C. for 5 hours using 10 vol% hydrogen gas (diluted with nitrogen) to obtain catalyst 2.
  • Aqueous solution 2 was obtained by dissolving 2.0011 g of cesium nitrate in 4.9936 g of distilled water. After 1.5130 g of aqueous solution 2 was added to 2.8595 g of catalyst 1 and mixed, it was dried at 90 ° C. overnight. To this dried mixture, 1.4367 g of the aqueous solution 2 was again added and mixed, and then dried at 90 ° C. overnight. The dried mixture was baked at 350 ° C. for 5 hours under a nitrogen stream, and then baked at 500 ° C. for 3 hours under an air stream. The calcined product was filled in an annular furnace and subjected to reduction treatment at 450 ° C. for 5 hours using 10 vol% hydrogen gas (diluted with nitrogen) to obtain Catalyst 3.
  • ⁇ Experimental example III-6 ⁇ ⁇ -alumina (manufactured by Sumitomo Chemical Co., Ltd.) was heat treated at 950 ° C. for 10 hours, pulverized, and dried at 120 ° C. overnight. By this heat treatment, the crystal phase of alumina was changed from the ⁇ phase to the ⁇ phase.
  • the amount of nickel supported on the catalyst 6 was 10% by mass.
  • Example III-7 Catalyst 7 was obtained in the same manner as in Experimental Example III-6 except that in Experimental Example III-6, 17.34 g of nickel nitrate hexahydrate was changed to 17.28 g of cobalt nitrate hexahydrate.
  • ⁇ Experimental example III-8 ⁇ ⁇ -alumina (manufactured by Sumitomo Chemical Co., Ltd.) was heat treated at 950 ° C. for 10 hours, pulverized, and dried at 120 ° C. overnight. By this heat treatment, the crystal phase of alumina was changed from the ⁇ phase to the ⁇ phase.
  • An aqueous solution prepared by dissolving 10.05 g of magnesium nitrate in 24.0 g of distilled water was added dropwise to 30 g of this heat treated alumina and mixed. The mixture was dried on a hot water bath and then calcined at 500 ° C. for 2 hours in an air stream to obtain heat treated alumina to which magnesium oxide was added.
  • Experimental Example III-10 >> In Experimental Example III-6, 17.34 g of nickel nitrate hexahydrate was changed to 6.61 g of nickel sulfate hexahydrate, and reduction treatment using 10 vol% hydrogen gas in the annular furnace was not performed. Produced a catalyst 10 in the same manner as in Experimental Example III-6.
  • the precipitate was filtered, washed with water, and dried overnight at 120 ° C.
  • the dried precipitate was pulverized, filled in an annular furnace, and reduced at 600 ° C. for 1 hour using 10 vol% hydrogen gas (diluted with nitrogen) to obtain catalyst 11.
  • Experimental Example III-12 A catalyst 12 was obtained in the same manner as in Experimental Example III-11 except that 34.89 g of nickel nitrate hexahydrate was changed to 34.92 g of cobalt nitrate hexahydrate in Experimental Example III-11.
  • the precipitate was filtered, washed with water, and dried overnight at 120 ° C.
  • the dried precipitate was pulverized, filled into an annular furnace, and reduced at 600 ° C. for 1 hour using 10 vol% hydrogen gas (diluted with nitrogen) to obtain catalyst 15.
  • the precipitate was filtered, washed with water, and dried overnight at 120 ° C.
  • the dried precipitate was pulverized, filled in an annular furnace, and reduced at 600 ° C. for 1 hour using 10 vol% hydrogen gas (diluted with nitrogen) to obtain catalyst 16.
  • the precipitate was filtered, washed with water, and dried overnight at 120 ° C.
  • the dried precipitate was pulverized, filled in an annular furnace, and reduced at 600 ° C. for 1 hour using 10 vol% hydrogen gas (diluted with nitrogen) to obtain catalyst 19.
  • the precipitate was filtered, washed with water, and dried overnight at 120 ° C.
  • the dried precipitate was pulverized, filled into an annular furnace, and reduced at 600 ° C. for 1 hour using 10 vol% hydrogen gas (diluted with nitrogen) to obtain catalyst 20.
  • the precipitate was filtered, washed with water, and dried overnight at 120 ° C.
  • the dried precipitate was pulverized, filled in an annular furnace, and reduced at 600 ° C. for 1 hour using 10 vol% hydrogen gas (diluted with nitrogen) to obtain catalyst 22.
  • Experimental Example III-24 4 g of the catalyst 12 prepared in Experimental Example III-12 was added to an aqueous solution in which 0.0295 g of cesium nitrate was dissolved in 20 mL of distilled water, heated to dryness in a hot water bath, and the catalyst 12 was impregnated with cesium nitrate. It was. The impregnation was dried at 120 ° C. overnight. The dried impregnated product was pulverized, filled in an annular furnace, and reduced at 600 ° C. for 1 hour using 10 vol% hydrogen gas (diluted with nitrogen) to obtain catalyst 24.
  • Example III-25 ⁇ A catalyst 25 was obtained in the same manner as in Experimental Example III-24 except that 0.0295 g of cesium nitrate was changed to 0.0593 g of cesium nitrate in Experimental Example III-24.
  • Example III-26 ⁇ A catalyst 26 was obtained in the same manner as in Experimental Example III-24 except that 0.0295 g of cesium nitrate was changed to 0.12 g of cesium nitrate in Experimental Example III-24.
  • Example III-27 A catalyst 27 was obtained in the same manner as in Experimental Example III-24 except that 0.0295 g of cesium nitrate was changed to 0.244 g of cesium nitrate in Experimental Example III-24.
  • Example III-29 ⁇ A catalyst 29 was obtained in the same manner as in Experimental Example III-24 except that 0.0295 g of cesium nitrate was changed to 0.652 g of cesium nitrate in Experimental Example III-24.
  • Experimental Example III-30 4 g of the catalyst 11 prepared in Experimental Example III-11 was added to an aqueous solution in which 0.0295 g of cesium nitrate was dissolved in 20 mL of distilled water, heated in a hot water bath to dryness, and the catalyst 11 was impregnated with cesium nitrate. It was. The impregnation was dried at 120 ° C. overnight. The dried impregnated product was pulverized, filled in an annular furnace, and reduced at 600 ° C. for 1 hour using 10 vol% hydrogen gas (diluted with nitrogen) to obtain catalyst 30.
  • Example III-31 To an aqueous solution in which 0.052 g of potassium nitrate was dissolved in 20 mL of distilled water, 4 g of the catalyst 12 prepared in Experimental Example III-12 was added and heated to dryness in a hot water bath, and the catalyst 12 was impregnated with potassium nitrate. The impregnation was dried at 120 ° C. overnight. The dried impregnated product was pulverized, filled in an annular furnace, and reduced at 600 ° C. for 1 hour using 10 vol% hydrogen gas (diluted with nitrogen) to obtain catalyst 31.
  • Example III-32 ⁇ A catalyst 32 was obtained in the same manner as in Experimental Example III-31 except that 0.052 g of potassium nitrate was changed to 0.104 g of potassium nitrate in Experimental Example III-31.
  • Example III-33 A catalyst 33 was obtained in the same manner as in Experimental Example III-31 except that 0.052 g of potassium nitrate was changed to 0.211 g of potassium nitrate in Experimental Example III-31.
  • Example III-34 4 g of the catalyst 12 prepared in Experimental Example III-12 was added to an aqueous solution in which 0.077 g of barium nitrate was dissolved in 20 mL of distilled water, and heated to dryness in a hot water bath to impregnate the catalyst 12 with barium nitrate. It was. The impregnation was dried at 120 ° C. overnight. The dried impregnated product was pulverized, filled in an annular furnace, and reduced at 600 ° C. for 1 hour using 10 vol% hydrogen gas (diluted with nitrogen) to obtain a catalyst 34.
  • Example III-35 A catalyst 35 was obtained in the same manner as in Experimental Example III-34 except that 0.077 g of barium nitrate was changed to 0.155 g of barium nitrate in Experimental Example III-34.
  • Example III-34 catalyst 36 was obtained in the same manner as in Example III-34, except that 0.077 g of barium nitrate was changed to 0.846 g of barium nitrate.
  • Example III-37 4 g of the catalyst 12 prepared in Experimental Example III-12 was added to an aqueous solution in which 0.127 g of strontium nitrate was dissolved in 20 mL of distilled water, and heated to dryness in a hot water bath to impregnate the catalyst 12 with strontium nitrate. It was. The impregnation was dried at 120 ° C. overnight. The dried impregnated product was pulverized, filled into an annular furnace, and reduced at 600 ° C. for 1 hour using 10 vol% hydrogen gas (diluted with nitrogen) to obtain catalyst 37.
  • Example III-38 4 g of the catalyst 13 prepared in Experimental Example III-13 was added to an aqueous solution in which 0.0593 g of cesium nitrate was dissolved in 20 mL of distilled water, and heated to dryness in a hot water bath to impregnate the catalyst 13 with cesium nitrate. It was. The impregnation was dried at 120 ° C. overnight. The dried impregnated product was pulverized, filled in an annular furnace, and reduced at 600 ° C. for 1 hour using 10 vol% hydrogen gas (diluted with nitrogen) to obtain a catalyst 38.
  • the ammonia decomposition rate is determined by the conditions of a space velocity of ammonia of 6,000 hr ⁇ 1 , a reaction temperature of 400 ° C., 450 ° C., 500 ° C., 550 ° C., 600 ° C., or 700 ° C., and a reaction pressure of 0.101325 MPa (normal pressure). Measured below (calculated by the following formula). The results are shown in Table 12.
  • the catalysts 1 to 38 were prepared with a high concentration of ammonia having a purity of 99.9% by volume or higher at a relatively low temperature of 400 to 600 ° C. and 6, It can be efficiently decomposed into nitrogen and hydrogen at a high space velocity of 000 h ⁇ 1 .
  • the catalysts 11, 12 and 15 to 37 are composed of cobalt or nickel which is an iron group metal and ceria, zirconia which is a metal oxide, a solid solution of ceria and zirconia, a solid solution of ceria and yttria, or ceria and lanthanum oxide. Therefore, the ammonia decomposition rate is relatively high.
  • the addition component cesium, potassium or barium is appropriately added to the solid solution of cobalt, which is an iron group metal, and ceria, which is a metal oxide, and zirconia.
  • Addition of a small amount (specifically, 2 to 4% by mass for cesium, about 1% by mass for potassium, and about 2% by mass for barium) improves the ammonia decomposition rate. I understand that.
  • the present invention relates to the decomposition of ammonia, and makes a great contribution in the environmental field in which ammonia-containing gas is treated and non-brominated, and in the energy field in which ammonia is decomposed into nitrogen and hydrogen to obtain hydrogen. It is what makes.

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JP2011224554A (ja) * 2010-03-31 2011-11-10 Nippon Shokubai Co Ltd アンモニア分解用触媒及び該触媒の製造方法、並びに該触媒を用いた水素製造方法
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EP2554257A4 (de) * 2010-03-31 2014-09-03 Nippon Catalytic Chem Ind Katalysator zur zersetzung von ammoniak, verfahren zur herstellung des katalysators und verfahren zur wasserstoffherstellung mithilfe des katalysators
EP2612706A4 (de) * 2010-08-31 2016-11-02 Hitachi Shipbuilding Eng Co Katalysator für ammoniakoxidation/ammoniakzersetzung
US9580309B2 (en) 2010-08-31 2017-02-28 Hitachi Zosen Corporation Ammonia oxidation/decomposition catalyst
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EP2332646A1 (de) 2011-06-15
KR101595963B1 (ko) 2016-02-19
KR20110055722A (ko) 2011-05-25
EP2332646B1 (de) 2020-07-15
US20110176988A1 (en) 2011-07-21
CN102159314B (zh) 2016-08-03
CN102159314A (zh) 2011-08-17

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